Production of polyurea copolymers from an alkylene diamine, a heteromembered alkylene diamine and a urea



Yanosuke Inaba, Fujisawa,

United States Patent PRODUCTION or l oLrunnA COPOLYMERS FROM AN ALKYLENEDIAMINE, A rmrano- MEMBERED ALKYLENE DIAMINE AND A UREA Kunihiko Miyake,Kamakura,

and Koji Kimoto and Goro Kimura, Fujisawa, Japan, assignors to ToyoKoatsu Industries, Inc, Tokyo, Japan, a corporation of Japan No Drawing.Filed Mar. 17, 1960, Ser. No. 15,515

Claims priority, application Japan Mar. 30, 1959 11 Claims. (Cl.260-4585) The present invention relates generally to improvements insynthetic thermoplastic polymers and it relates more particularly to apolyurea copolymer and to a method for producing the same.

Fibers spun of polyurea polymers having linear alkylene groups possessexcellent chemical and physical properties. They have a high tenacity,good elastic recovery and Youngs modulus, good chemical resistance andother desirable characteristics. By reason of their high melting pointsand relatively low decomposition temperatures, however, themelt-spinning of these polyurea polymers into fibers possesses manydisadvantages and drawbacks and is rather difiicult on a commercialscale as compared with other synthetic fibers. This is particularly truewhere the alkylene radicals have a small number of carbon atoms and itis practically impossible to spin into fibers polyurea polymers havingless than six carbons in their alkylene radicals. Whilst polyureapolymers having six or more carbons in their alkylene radicals may bemelt-spun on a commercial scale, the resulting fiber is worsened indyeability with an increase in the carbons of the alkylene radical.

In the meanwhile, fibers spun of polyurea polymers havinghetero-membered alkylene radicals with at least one ether group (O--) orone thio-ether group (S) possess excellent characteristics in dyeabilityand resistance to heat, but they have a relatively low Youngs modulus,and consequently they lack in wool touch when woven into fabrics.

It is, therefore, a principal object of the present invention to providean improved polyurea copolymer and a process for producing the same.

Another object of the present invention is to provide an improvedpolyurea copolymer with spinnability and good dyeability and a method ofproducing the same.

Still another object of the present invention is to provide an improvedpolyurea copolymer of the above nature which may be spun into fibershaving superior physical and chemical properties.

The inventors have succeeded in eliminating the drawbacks innate in theabove polyureas by producing a polyurea copolymer having superior andhighly desirable chemical and physical properties in the followingmanner; a diamide compound such as urea, thiourea, alkylene diurea ordithiourea, at least one member of the group consisting of linearalkylene diamines having alkylene radicals with at least six carbons andtheir carbonates, and at least one member of the group consisting ofhetero-membered alkylene diamines having at least one ether group or onethioether group wherein each alkylene radical has two to eight carbonsand their carbonates, are reacted at a polycondensation temperature. Thehetero-membered alkylene diamines having at least one ether group or onethioether group are compounds represented by the formulae H N-R -OR NHand similar compounds and their carbonates in which R R and R arealkylene radicals having two to eight 3,133,897 Patented May 19, 1964 2carbons. As for the linear alkylene diamines may be employed in additionto those having six to nine carbons given in the following examplesdecamethylenediamine, undecamethylenediamine, dodecamethylenediamine andtheir carbonates.

To prepare the polyurea copolymer, a mixture of at least one linearalkylene diamine and at least one heteromembered alkylene diamine havingat least one ether group or one thioether group is further mixed withpreferably an approximately equimolecular ratio of the diamide compoundand is preferably though not necessarily dissolved in a solvent andheated in an inert gas atmosphere such as pure nitrogen at temperaturesstarting at C. and raising up to 260 C. over a period of time sufiicientto conclude polycondensation. As for the solvent are employed water,phenol and metacresol, of which water is preferred. The total amount oflinear alkylene diamines and the hetero-membered alkylene diamines maybe employed in 1-1.5 mols to 1 mol diamide compound, preferably in 11.04mols. Actually a process comprising a combination of the following threestages may be used; a first stage wherein a mixture of at least onelinear alkylene diamine and at least one hetero-membered alkylenediamine having at least one ether group or one thioether group isfurther mixed with preferably an approximately equimolecular ratio ofthe diamide compound and is preferably though not necessarily dissolvedin the aforementioned solvent and heated in an inert gas atmosphere suchas pure nitrogen at a temperature in the range between 80 C. and C. fora period of time sufiicient to substantially produce two molecularcondensation products in each of which one molecule of urea is combinedwith a molecule of one of the alkylene diamines and the hetero-memberedalkylene diamines employed. This is illustrated by the followingequation:

wherein R stands for the alkylene radicals and/ or the hetero-memberedalkylene radicals employed. In a second stage the two molecularcondensation products are heated at a temperature in the range between130 C. and 240 C. for a period of time suificient to substantiallyproduce half polymers wherein both terminal radicals are amino radicals.

In a third stage the temperature is gradually raised to 230 C.-260 C.with the distillation off of the solvent when it is employed. Theheating is continued at the above temperature and under reduced pressurefor a period of time sufiicient to conclude the polycondensationreaction. In the reaction under reduced pressure a complete removal ofthe residual solvent as well as of the linear alkylene diamines and thehetero-membered alkylene diamines formed as by-products by amineexchange reactions which occurred to the half-polymer is carried out.The reaction under reduced pressure in the present invention isindispensable for raising the polymerization grade to such an extent asto enable the resulting polyurea copolymer to be obtained to be spuninto fibers of excellent characteristics.

It is preferable to add to the reaction mixture in any stage prior tothe third stage a viscosity stabilizer such as an alkyl-monoamide, anN-acylalkylene-diamine or a monobasic acid in which the alkyl or acylradical has at least three and preferably six or more carbons in orderto inhibit the so-called urea-dearrangement which would take place byheating the polyurea polymers at a high temperature. The stabilizer maybe employed in 0.005-0.05 mol to 1 mol diamide compound, preferably in0.01-0.025 mol.

The copolymer produced in accordance with the present process ischaracterized by its relatively low melting point, high decompositiontemperature and excellent meltspinning properties. Fibers spun of thecopolymer possess excellent dyeing properties, high tenacity, goodYoungs modulus, elastic recovery and other chemical and physicalproperties. The properties of the copolymer may be controlled by varyingthe relative proportions of the linear alkylene diamines and thehetero-membered alkylene diamines. For example, when a linear alkylenediamine and a hetero-membered alkylene diamine are employed in anequimolecular ratio, a copolymer of low melting and crystallinity isobtained. As the linear alkylene diamine proportion is increased, theYoungs modulus of the copolymer approaches that of the polyurea polymerof the corresponding alkylene diamine while the copolymer stillmaintains excellent dyeability particularly with acid dyestuffs. Thefollowing table sets forth the relative dyeing velocities of variousfibers and fibers produced in accordance with the present invention,employing acid dyes and dispersed dyes at a dyeing temperature of 100concentration of 3%, min.

the data being given in mg./gram Arbitrary Velocity Constant (mg/grammin) Table 1 M01 ratio linear alkylene: alkylene ether=1:1.

The following examples, in which the parts are given by weight, areillustrative of the present invention:

EXAMPLE 1 A solution of 8 1 parts of hexamethylene diamine, 60 parts of5-5'-diamino-dipentylether, 60 par-ts of urea and 2.6 parts of palmiticacid amide (molal ratio- 70232210021) in three times by weight ofm-cresol was heated at 120 C. for 8 hours in an inert gas atmosphere ofsubstantially pure nitrogen. Thereafter, the heating was continued for 4hours at 180 C. resulting in the evolution of ammonia and thecondensation of the reactants, the mass gradually assuming a viscousstate. The temperature was then raised to 250 C. and the pressurereduced to distill off the solvent and condensation copolymerizationreaction completed to provide the molten copolymer which may be readilyspun into fibers. The resultant copolymer resin had an intrinsicviscosity in m-cresol of 0.7 to 0.8 and a melting point of 190 C. to 195C. The fibers spun from the copolymer resin had a tenacity of 4 to 5grams per denier, a You-ngs modulus of 350 kg./cm. and a dyeing velocityat a temperature of 100 C., a dye concentration of 3%, a bath ratio of100 and a pH of 2 fifty times that of polycaprolactam.

EXAMPLE 2 A solution of 150 parts of the carbonate ofoctamethylene-diamine, 45 parts of the carbonate of4.4-diaminodibutyl-ether, 60 parts of urea and 2.6 parts of palmiticacid (molal ratio80:22:100:1) in 40 parts of water was heated for 40hours at 100 C. in the presence of a substantially pure nitrogenatmosphere. The temperature was then gradually raised to 240 C. with thedistillation of Water, ammonia and carbon dioxide being released and themass becoming viscous. The heating was continued at 240 C. for 2 hoursat a reduced pressure to complete the condensation polymerization, theresulting molten copolymer being readily spinnable into fibers, andhaving a melting point of 210 C. and an intrinsic viscosity in m-cresolof 0.8 to 0.9. The copolymer fiber C., a bath ratio of 100 and a dye hada tenacity of 4 grams per denier, a Youngs modulus of 400 kg./cm. and adyeing velocity of 60 times that of polycaprolactam under the dyeingconditions set forth in Example 1.

EXAMTLE 3 A solution of 20 parts of nonamethylenediamine, 142 parts of3.5 diaminopropyl-amyl-ether, 132 parts of methylene diurea and 5.1parts of palmitic acid (molal ratio-12:90: 100:2) in 100 parts of waterwas heated for 35 hours at 100 C. and the temperature thereafter raisedto 230 C., with the distillation of water and the evolution of ammonia,the reaction mass becoming viscous. The reaction was effected in thepresence of a substantially pure nitrogen atmosphere. The heating of themass was continued for 2 hours at 230 C. and at a pressure of 1 mm. ofmercury to produce a readily spinnable copolymer having an intrinsicviscosity in m-cresol of 0.6 to 0.8. The resin had a low crystallinityand could be easily molded and formed into film and the fibers formedfrom the resin dyed deeply and uniformly with acid dyes.

EXAMPLE 4 A mixture of 77 parts of octamethylene diamine, 49 parts ofhexamethylene diamine, 20 parts of 5.5-diamino diamyl sulphide, 60 partsof urea and 1.2 parts of caproic acid (molal ratio: 50:42:10:100:1) wereheated in a vessel in a nitrogen atmosphere for 10 hours, thetemperature being gradually raised from 120 C. to 240 C. Ammonia wasreleased and a viscous mass resulted which was further heated at 240 'C.for three hours at a pressure of 1 mm. of mercury to complete thecondensation polymerization and produce a readily spinnable copolymerhaving a melting point of 210 C. to 215 C. and an intrinsic viscosity inm-cresol of 0.6 to 0.7. The fiber spun from the copolymer had a tenacityof 4 to 5 grams per denier, excellent crispation and a dyeing velocityapproximately 30 times that of polycaprolactam under the dyeingconditions set forth in Example 1.

EXAMPLE 5 parts of hexamethylene diamine, 41 parts of ethylene glycolbis (4-amino butyl ether), 60 parts of urea and 2.6 parts of N-caproylnonamethylene diamine (molal ratio-82:20: 1) were dissolved in 80 partsof phenol at C. The reaction proceeded for 8 hours in the presence of anitrogen atmosphere, the temperature being gradually increased andammonia being vigorously released. Upon the diminution of the release ofammonia the temperature was raised to 210 C. to distill the phenol andthen to 250 C. to produce a viscous mass. The heating was continued fortwo hours at 250 C. and at a pressure of 1 mm. of mercury to completethe condensation polymerization and produce a copolymer having anintrinsic viscosity in m-cresol of 0.6 to 0.7 and other propertiessimilar to those of the copolymer in accordance with Example 1.

EXAMPLE 6 40 parts of the carbonate of heptamethylene diamine, 180 partsof the carbonate of 4.4'-diamino dibutyl ether, 76 parts of thiourea and2.6 parts of palrnitic acid amide (molal ratio-21:81:100:1) were placedin a vessel through which nitrogen Was circulated to exclude air. Thevessel was heated to 90 C. for 40 hours to effect the solution of thereactants and the reaction permitted to proceed. The temperature wasraised to 180 C. over i chip, could be easily molded and possessed theproperties of the copolymer produced in accordance with Example 4.

EXAMPLE 7 87 parts of octamethylene diamine, 84 parts of 5.5- diaminodiamyl sulphide, 76 parts of thiourea and 3 parts of pelargonic acid(molal ratio-60:4l 100:2) were heated for 6 hours at 120 C. in 300 partsof phenol in a nitrogen atmosphere to efiect the solution thereof. Thetemperature was then raised to between 160 C. and 180 C. with theaccompanying violent release of ammonia. Upon the diminution of theammonia evolution the temperature was raised to distill off the phenoland then further raised and maintained for about three hours at atemperature of 250 C. and at the reduced pressure of 1 mm. of mercury tocomplete the polycondensation to produce a molten copolymer of goodspinnability and having a melting point of 210 C. to 215 C. A fibermeltspun from the copolymer had a tenacity of 5 to 6 grams per denier,good resistance to sunlight and alkalis, and could be deeply anduniformly dyed with various types of dyes.

The following is a table of some of the properties of polynreacopolymers produced in accordance with the present invention as comparedwith other synthetic fibers:

and carbonates thereof, wherein R and R are alkylene groups having from1 to 5 carbon atoms and R is an alkylene group having 4 carbon atoms.(c) a diamide selected from the group consisting of urea, thiourea andmethylene diurea, to substantially produce two molecular condensationproducts of a+c and b+c, continuing heating in a second stage saidcondensation products at a temperature of 130 C. to 230 C. until theevolution of ammonia substantially ceases and polymers are producedwherein both terminal radicals are amino radicals and thereafter raisingthe temperature and heating in a third stage said polymers at atemperature in the range of from 230 C. to 260 C. at a pressure ofapproximately 1 mm. Hg from 2 to 3 hours to produce said polyureacopolymers.

2. The process according to claim 1, wherein the reactants are initiallymixed with a viscosity stabilizer selected from the group consisting ofalkylene monoamide, N-acyl alkylene diamine, alkyl monobasic acids, andacyl monobasic acids, wherein said monobasic acids have at least 3carbon atoms.

3. The process according to claim 1 wherein the mole ratio of amines todiamide is maintained in the range of from 1l.5:1.

4. The process of claim 1 wherein (a) is hexamethylen Properties 0Hetero-Membered Polyurea co-Polymers Recovery Decom- Dyeability; Molalof elasticity, Melting position Resistance Velocity Components Ratio ofpercent Point, Temperaagainst Constant Com- (elonga- C. ture, Abrasionof Dyeing ponents tion C. Time 2 k(mg./g.

44 diamino dibutylether 100 216 278 270-400 2, 000 4.4 diaminodibutylether and C diamine 4 :1 97 203 277 260-400 1, 900 4.4 diaminodibutylether and C diamine 4 :1 90 205 275 250-400 1, 700 C9 diamineonly 87 236 282 100-180 15 Nylon 6 100 230 higher 250-500 32 than 300Terylen 80 -100 0. 1

l Instantaneous recovery of elasticity after 8% elongation release.

2 Resistance against abrasion: The time required to break a fiber of1000 deniers with a 500 g. weight by abrasion against a metal surface.

3 Dyeability: With acid colors, Mitsui Brilliant Mllllllg Red in a 3ratio of 100 for 1 hr.

s-x debit-Is s: Saturated color concentration in fiber x: Colorconcentration in fiber after 1 hr. from start k: Velocity constant ofdyeing As many apparently widely different embodiments of this inventionmay be made without departing from the spirit and scope thereof, it isto be understood that the present invention is not limited to thespecific embodiments thereof except as defined in the appended claims.

What is claimed is:

1. A process for the manufacture of polyurea copolymers withhetero-membered alkylene urea having good spinnability comprisingreacting in a first stage at a temperature in the range of 80 C. to 130C. to elfect solution thereof in an inert atmosphere a mixturecontaining:

(a) at least one and not more than two members of the group consistingof linear alkylene diamines having from 6 to 9 carbon atoms in thealkylene radical and carbonates thereof,

(b) a member selected from the group consisting of hetero-memberedlinear alkylene diamines having the formula H2NR1-OR2 NH2,

solution at 0., a pH of 2, and a bath diamine, (b) is5,5'-diarnino-dipentyl ether and (c) is urea.

5. The process of claim 1 wherein (a) is the carbonate of octamethylenediamine, (b) is the carbonate of 4,4-diarnino dibutyl ether and (c) isurea. 6. The process of claim 1 wherein (a) is nonamethylenediamine (b)is 3,5'-diaminopropyl-amyl ether and (c) is methylene diurea. 7. Theprocess of claim 1 wherein (a) is a mixture of octamethylene diamine andhexamethylene diamine, (b) is 5,5'-diamino diamyl sulfide and (c) isurea. 8. The process of claim 1 wherein (a) is hexamethylene diamine,(b) is ethylene glycol bis(4-amino butyl ether) and (c) is urea. 9. Theprocess of claim 1 wherein (a) is the carbonate of heptamethylenediamine, (b) is the carbonate of 4,4'-diamino dibutyl ether and (c) isthiourea. 10. The process of claim 1 wherein (a) is octamethylenediamine, (b) is 5,5'-diamino diamyl sulfide and (c) is thiourea. 11. Theprocess according to claim 1 wherein the reaction is initiated in asolvent selected from the group consisting of Water, phenol andmetacresol.

2,852,494 Lehmann Sept. 16, 1958 8 FOREIGN PATENTS Great Britain Mar. 7,1949 Great Britain Dec. 9, 1940 Great Britain Mar. 14, 1941 GreatBritain Mar. 7, 1949

1. A PROCESS FOR THE MANUFACTURE OF POLYUREA COPOLYMERS WITHHETERO-MEMBERED ALKYLENE UREA HAVING GOOD SPINNABILITY COMPRISINGREACTING IN A FIRST STAGE AT A TEMPERATURE IN THE RANGE OF 80*C. TO130*C. TO EFFECT SOLUTION THEREOF IN AN INERT ATMOSPHERE A MIXTURECONTAINING: (A) AT LEAST ONE AND NOT MORE THAN TWO MEMBERS OF THE GROUPCONSISTING OF LINEAR ALKYLENE DIAMINES HAVING FROM 6 TO 9 CARBON ATOMSIN THE ALKYLENE RADICAL AND CARBONATES THEREOF, (B) A MEMBER SELECTEDFROM THE GROUP CONSISTING OF HETERO-MEMBERED LINEAR ALKYLENE DIAMINESHAVING THE FORMULA H2N-R1-O-R2-NH2,
 2. THE PROCESS ACCORDING TO CLAIM 1,WHEREIN THE REACTANTS ARE INITALLY MIXED WITH A VISCOSITY STABILIZERSELECTED FROM THE GROUP CONSISTING OF ALKYLENE MONOAMIDE, N-ACYLALKYLENE DIAMINE, ALKYL MONOBASIC ACIDS, AND ACYL MONOBASIC ACIDS,WHEREIN SAID MONBASIC ACIDS HAVE AT LEAST 3 CARBON ATOMS.